CN1497007A - Material and method for preparing insertion laminated material - Google Patents

Material and method for preparing insertion laminated material Download PDF

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Publication number
CN1497007A
CN1497007A CNA031602592A CN03160259A CN1497007A CN 1497007 A CN1497007 A CN 1497007A CN A031602592 A CNA031602592 A CN A031602592A CN 03160259 A CN03160259 A CN 03160259A CN 1497007 A CN1497007 A CN 1497007A
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particle
medium
poly
stratified material
stratified
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王锦山
布兰顿
王晓茹
S·陈
T·N·布兰顿
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Provided is an image forming element having improved mechanical strength and other physical characteristics, and comprising a flexible thermoplastic base. A sprayed material comprises a sprayed layered material with particles having a diameter of <=3 [mu]m. A practicing embodiment includes an article comprising a matrix and the sprayed layered material with a polymer particle dispersed in a medium. A producing method of these materials comprises mixing and grinding particles, and emulsifying the polymer supported in a solvent with a surfactant. As an alternative method, a producing method of a nanocomposite material comprising forming spraying agent particles by incorporating a non-dispersible emulsion polymerization monomer in a medium with a dispersible surfactant in the medium, and then producing the nanocomposite material therefrom, is disclosed.

Description

The material and the method for preparation intercalation stratified material
Technical field
The present invention relates to use diameter is that 3 microns or littler polymer beads are with stratified material intercalation method.
Background technology
In more than ten years in the past, well set up as the method that additive improves the polymer materials performance about using inorganic nanoparticles.Since the research work of centralab of Toyota (Toyota CentralResearch Laboratories), polymer-clay nanocomposites has caused the extensive interest of different industrial trades.The physicals of this nano composite material uniqueness is also utilized by these industrial sectors (as automotive industry, packing business, plastics industry).These performances comprise the mechanical property of improvement such as coefficient of elasticity, tension force, thermal property such as coefficient of linear expansion and heat-drawn wire, barrier propterty such as oxygen and water vapour transmitance, flame retardant properties, melt, solvent absorbing etc.Some relevant prior aries exemplify as follows: United States Patent (USP) 4,739,007,4,810,734,4,894,411,5,102,948,5,164,440,5,164,460,5,248,720,5,854,326 and 6,034,163.
In general, it is to be less than 20vol% by adding that the physicals of these nano composite materials improves, and what normally be less than 10vol% inorganicly realizes this inorganic clay or organo-clay of being generally mutually mutually.Though it is these improve seemingly relevant with the nanometer scale dispersion of inorganic phase a kind of universal phenomenon, also inconsistent for the degree of all its raisings of polymkeric substance.This performance improves form and the degree of scatter that depends on inorganic phase in the polymeric matrices to a great extent by inference.
Think that the clay in the ideal polymer-clay nanocomposites has three kinds of structures (1) clay seam, its clay particle is assembled Face to face and do not insert organism in clay lattice, (2) insert clay, wherein the insertion of each polymer chain causes clay lattice to be expanded to the equilibrium spacing of thermodynamic definitions, but the order that in lattice, keeps long distance, (3) clay that peels off, wherein because polymkeric substance extensively infiltrates into clay lattice and peeling off subsequently thereof, single clay thin layer is suspended in the polymkeric substance randomly.Use the above-mentioned back two kinds of structures expection of this paper to realize that the performance of the maximum of polymer-clay nanocomposites improves.
The material of the existing clay of making great efforts to be poured into the development insertion in a large number and/or peeling off and other insert the raw material and the method for inorganic materials.Except inserting and/or peeling off, clay is also tackled its residing polymeric matrices that distributes mutually and is had compatibility.The challenge that realizes these targets is from the following fact: promptly unmodified surface of clay is hydrophilic, and technical important a large amount of thermoplastic polymers are hydrophobic.Though can with organic molecule clay be inserted by many methods, make clay compatibility in polymeric matrix of these insertions still have many difficulties to distribute equably.Industrial, clay supplier generally only provides the clay of insertion, and final user's challenge is to select to make the compatible material and the method for thermoplastics of these clays and their selections.For the final user, this chosen process comprises with considerable test of development cost experience and mistake.Because the clay in the matrix polymer inserts with compatibilized in matrix polymer and relates generally at least two kinds of different materials, method and positions, thereby it is impaired to comprise the total cost of production of polymer-clay nanocomposites.
Most insertion clay interacts by anionic clay and cats product and produces, and described cats product comprises the sulfonium derivative of compound such as ammonium (primary, the second month in a season, uncle and quaternary ammonium), phosphorus or fat, fragrance or aryl aliphatic amide, phosphuret-(t)ed hydrogen, sulfide etc.These ions can by with clay in the metallic cation that exists carry out ion-exchange and cause clay to insert to reach charge balance.Yet these surfactant molecules may be degraded in the melting process of back, and this just makes processing temperature and the selection of polymeric matrix has been subjected to considerable restraint.In addition, the insertion of tensio-active agent tends to introduce moisture, and this need remove by drying step subsequently.
Opposite with the small molecular weight tensio-active agent, known in the state of the art in clay the insertion polymerization thing.The main at present two kinds of insertion methods----of using are inserted suitable monomers polymerization then (as in-situ polymerization, seeing people such as A.Okada, Polym Prep., Vol.28,447,1987) or are inserted monomer/polymer by solution.Polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) have been applied to inserting in the clay seam, and obtain some successes.As people such as Levy, at " interlayer adsorption of pvp onmontmorillonite ", (Journal of Colloid and Interface Science, vol 50 (3), 442,1975) described in, attempted, attempted then adsorbing PVP by making its PVP/ ethanol/water solution contact and change water consumption with 1% by PVP is adsorbed onto between the clay layer of single ion polynite.With after the PVP/ ethanol/water solution contacts, only the expansion of sodium type polynite surpasses 20 dust fundamental spaces.The research of GREENLAND (Adsorption of polyvinyl alcohol by montmorillonite, journalof colloid science, vol.18.647-667 (1963)) finds that the absorption of PVA in polynite depends on the concentration of PVA in the solution, find, have only polymer weight concentration when 1% order of magnitude, could realize efficient absorption.But this method is owing to also need drying to remove the restriction of desolvating thereby do not do further effort towards the industrialization direction after being inserted.People (New PolymerElectrolyte Nanocomposites:Melt intercalation of polyethyleneoxide in mica typesilicates in nearest research such as Richard Vaia, Adv.Materials, 7 (2), 154-156,1995,), by 80 ℃ down heating 2-6 hour to realize 17.7 d-spacing PEO is inserted into Na-polynite and Li-polynite.Degree of inserting and coming to the same thing by the solution gained.(V.Mehrotra，E.P.Giannelis，Solid?State?Commun，77，155，1911)。In addition, nearest research work (US5,804,613) relates to the adsorption that is selected from the following monomer organic compound with at least one carbonyl functional group: carboxylic acid and salt thereof, poly carboxylic acid and salt thereof, aldehyde, ketone or their mixture.Similarly, US5,880,197 discuss the insertion monomer that use contains amine or amide functional group or its mixture.In these patents and other are thought similar patent, be inserted in medium such as the water and under the clay concentration of extremely dilution, carry out, cause it before the fusion step, to need to finish expensive drying step.
For further promoting layer from and prevent the reunion of clay particle, it is compatible with the matrix polymer of wherein introducing to require these to insert clays.This can and introduce compatibilized or coupling reagent is realized by careful selection, and described reagent is by advantageously combining with surface of clay bonded part with matrix polymer or interactional another part is formed.Consistency between matrix polymer and the clay particle is guaranteed favourable interaction, thereby promotes to insert Dispersion of Clay in the matrix polymer.Effective compatibilized causes clay particle to be evenly dispersed in the typical hydrophobic matrix polymkeric substance and/or improvement is peeled off or the leafing clay.Known typical agents comprises big class material such as organic silane, organic zirconium hydrochlorate, organic titanate coupler in the present technique.But the selection of compatibilized reagent is depended on matrix polymer to a great extent and is used to insert the specific components of clay, because compatilizer must be as the two connection.
By the research present technique, be clear that shortage instructs about the routine of selecting insertion of particular substrate polymkeric substance and clay bonded and compatilizer.Even can identify this two kinds of necessary components by test and error, they are also introduced in the presence of water as two kinds of isolating entities usually, also finally combine with matrix polymer at independent position during the melt-processed nano composite material so that batch processing mode is dry then.So loaded down with trivial details processing obviously increases the cost of developing and making the finished product that comprise this nano composite material.Present technique presses for and is used to develop the comprehensive strategic of better material and method to overcome some above-mentioned defective.
Image-forming component applies image forming material such as photosensitive material as comprise a kind of flexible thermoplastic matrix as photograph component on this matrix.This thermoplastic matrix is generally made as polyethylene terephthalate (PET), Polyethylene Naphthalate (PEN), cellulosetri-acetate (TAC) by the derivative of polyester.Film, the film printing film that is used for colour, black-and-white photography is the example of image forming medium that comprises the flexible plastic matrix of spool form.Anti-curling but the attribute of bad mechanical strength after TAC has high-clarity and handles.On the other hand, PET has good physical strength and manufacturability, but its curling undesirable after handling.Preceding two attributes make PET be more suitable for the film thinning, make it can have bigger picture for the same thin film length.But the film thinning causes the physical strength loss.Rigidity roughly descends with the cubic root of film thickness.And the sensitive materials that applies on the matrix in the hydrophilic gel vehicle shrinks when drying and curl towards the emulsion direction.Need a kind of thin but hard to the matrix that is enough to resist the stress that causes owing to convergent force.Also film at high temperature to be offset during use.Therefore, thus the transparent film matrix that has good thermal capacitance to have good spatial stability will be unusual ideal.In the application of many covering materials, use the micron particle and the nano particle of polymkeric substance.But mechanism's intensity of these polymer materialss is sometimes less than ideal tensile strength.
A kind of flexible thermoplastic matrix that contains mechanism's intensity with improvement and other physicals need be provided.
Summary of the invention
The present invention relates to a kind of intercalation material, this intercalation material contains a kind of particulate stratified material that diameter is equal to or less than 3 microns that inserts.Another embodiment of the invention comprises a kind of object that contains matrix and insert the stratified material that is dispersed in the polymer beads in the medium.Further embodiment is the method for preparing nano composite material that comprises following steps: prepare a kind of particle, this particle is mixed with stratified material in being dispersed in medium, and stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.The present invention comprises that also another kind is used to prepare the method for nano composite material, this method comprises the following steps: to prepare a kind of particle by mixed emulsion polymerization single polymerization monomer and the tensio-active agent that can be dispersed in the medium, wherein this monomer can not be scattered in this medium, this particle and the stratified material that is dispersed in this medium are mixed, and this stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.The another kind of method that prepare nano composite material comprises the following steps: to grind this polymkeric substance and can be distributed to tensio-active agent in this medium to form a kind of particle that is dispersed in this medium in polymkeric substance can not the dispersive medium, this particle is mixed with stratified material in can being distributed to this medium, and this stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.In addition, the another kind of method for preparing nano composite material comprises the following steps: to make with tensio-active agent in polymkeric substance can not the dispersive medium solvent-laden polymer emulsified, and remove and desolvate to form a kind of particle, this particle and the stratified material that can be distributed in this medium are mixed, and this stratified material carries out intercalation to produce a kind of nano composite material, and wherein this particulate diameter is equal to or less than 3 microns.
The present invention has many advantages, but in not every advantages to the single embodiment.The nano composite material that comprises polymeric matrix and stratified material is used micron particle and nano particle, and it can be aqueous, environment amenable system, and need not further carry out any processing and use in most application.Above nano composite material can also or add salt by drying, heating and easily be converted into solid.Another advantage of using micron, nano particle is to be easy to produce, and need not to melt or use specific installation.
The present invention can advantageously provide a kind of method of making the nano composite material of polymeric matrix and stratified material.Particularly, the present invention can provide a kind of method for preparing the nano composite material that contains polymeric matrix and stratified material by hybrid microscale in solution and nano particle and stratified material.But the present invention can provide stratified material by micron or nano particle intercalation.The present invention can also provide insert micron or the stratified material of nano particle and the nano composite material of polymeric matrix or intercalation material a kind of comprising, and this material can be attached in polymkeric substance-stratified material nano composite material effectively.These polymer beads-stratified material nano composite material can be incorporated in the object of engineering application, and these objects have physicals such as modulus, tensile strength, toughness, shock-resistance, electric conductivity, heat-drawn wire, thermal linear expansion coefficient, resistivity against fire, oxygen and the water vapour barrier property etc. of improvement.Putting multiplex (MUX) industry department such as automobile, packing, battery, makeup, the aerial application of boat to have set forth this object in such as following document: " Polymer-Clay nanocomposites " Ed.T.J.Pinnavia and G.W.Beall for example, John Wiley﹠amp; Sons, Ltd.Publishers.
Some specific embodiments of the present invention also has other about insert/peel off the advantage of stratified material with micron or nano particle, wherein can easily realize being connected of matrix polymer and stratified material.The finished product can be the nano composite materials that contains sphere polymers particulate and stratified material, perhaps contain the polymer chain particle of elongation and the nano composite material of stratified material.Described particle can comprise by water-soluble or oil-soluble polymers water-soluble or that oil soluble surfactant is stable.These particles have and easily enter the stratified material lattice and make stratified material intercalation ability.Above-mentioned micron or nano particle can also comprise the structural unit compatible with another kind of matrix polymer, and add intercalation material in this matrix polymer.The stable particle of functional surface promoting agent can guarantee that grain fraction inserts/peel off stratified material, and another component or the functional group of adhering to make the intercalation stratified material compatible with matrix polymer.Therefore, two kinds about effectively with in the stratified material discrete particles to form ideal polymkeric substance-stratified material nano composite material, promptly stratified material insert/peel off with compatibilized the ideal standard can used functional surface promoting agent be met among the present invention by selecting.
The another one advantage of some specific embodiments of the present invention comes from the following fact: stratified material, particle and matrix polymer can one step combination in suitable solution, thereby generally increase the efficient of manufacturing process greatly.
In addition, the present invention instructs a kind of common strategy, wherein can revise the particulate chemistry according to the selection of stratified material and particular substrate polymkeric substance.Can easily control particle size to satisfy processing conditions, require as multiple physicals as temperature, shearing force, viscosity and product.
Description of drawings
Fig. 1 illustration P4 among the embodiment 8: the L2 ratio is 95: 5 a XRD figure.
Fig. 2 illustration P4 among the embodiment 8: the L2 ratio is 95: 5 a TEM image.
Fig. 3 illustration P3 among the embodiment 11: the L1 ratio is 95: 5 A (L1) and an XRD figure (B).
Embodiment
No matter when described term has following implication:
" nano composite material " means a kind of matrix material, and wherein at least a component comprises a kind of inorganic phase, as montmorillonite layered material, its at least the one dimension size at 0.1nm in the scope of 100nm.
" plate " means a kind of like this particle, and its two comparable sizes are obviously greater than third dimension size, and for example this particulate length and width have comparable size, but the order of magnitude is greater than particulate thickness.
" stratified material " means for example polynite of inorganic materials into a plurality of adjacent key coat forms.
" thin layer " means single layer in the stratified material
" insertion " refers to insert one or more foreign molecules or part foreign molecules between thin layer and stratified material, adopts x-ray diffraction technique to detect usually, and as United States Patent (USP) 5,891,611 (the 5th hurdle the 10th walks to the 7th hurdle the 23rd row) are described.
" inset " means the foreign molecules that inserts between the thin layer of aforementioned stratified material.
" insertion " refers to have the stratified material that inserts and/or peel off to the small part experience.
" peel off " or " leafing " refers to that single Thin-layer separation becomes the disordered structure without any stacked order.
" organo-metallic stratified material " refers to by organic molecule modified layered material.
" intercalation (splayed) " stratified material is defined as no any stratified material, the material that peels off fully of no any insertion degree and stratified material that inserts simultaneously and peel off of inserting fully that peels off degree, comprises unordered stratified material.
" intercalation (splaying) " refers to the separation of the layer of stratified material, arranges for still keeping lattice types as this separation degree in insertion, and perhaps this separation degree is the point that crystalline network is expanded to the crystalline network loss in peeling off.
" intercalator " refers to be used for the material of intercalation stratified material, as polymer beads.
The intercalation material of the present invention's preparation can comprise that insertion this paper is called the particulate stratified material of intercalator, and the diameter of described intercalator is equal to or less than 3 microns.In an embodiment preferred of the present invention, this particle can be to be of a size of 5nm to 100 μ m, the polymer beads of preferred 10nm to 2 μ m.In preferred embodiments, polymerization intercalator material is micron particle or nano particle.Be purpose of the present invention, micron particle is that diameter is the aggregated particles of 0.5-3 micron.Be the object of the invention, nano particle is a diameter less than 0.5 micron polymer beads.The intercalator particle can be atresia or porous particle.Particle can be the combination of any form, shape or form and shape, comprises porous micron or nano particle and core-shell particles.The intercalation stratified material can form nano composite material, and this nano composite material can be used separately or mix the new nano composite material of formation with additional polymeric matrix as total lot amount.
Further notice intercalation or stratified material can with particle, particularly polymer beads interacts in a particular manner.Polymkeric substance itself can be ball, class pearl form, and its diameter range is～30-80nm.Can find that the intercalation of stratified material or leafing thin layer attached on the polymer beads that also is called pearl, the surface, perhaps are clipped between the pearl, wherein intercalation or leafing thin layer vertically and the sphere tangent.
The intercalator micro-/ nano particle that uses among the present invention can prepare by two kinds of basal components of combination at least: at least a stablizer or dispersion agent are (as McCutcheon ' s volume1:Emulsifiers anddetergents, 1995, North American Edition, Manufacturing Confectioner PublishingCompany, 1995 is defined) and at least a polymkeric substance.In one embodiment, in fact polymkeric substance can comprise polymer monomer.
Any particle that can be used to form the present invention's use by some stablizer stable polymer.These polymkeric substance include but not limited to following polymers: aliphatic series or aromatic polyester, aliphatic series or aromatic poly, polyimide, urethane, polyethers, polycarbonate, polyolefine, poly-(methyl methacrylate), polystyrene, poly-p-methylstyrene, poly-tertiary butyl acrylamide, poly-(vinylbenzene-altogether-methyl methacrylate), poly-(vinylbenzene-altogether-tertiary butyl acrylamide), poly-(methyl methacrylate-altogether-tertiary butyl acrylamide) and the homopolymer of from following material, deriving out: methylacrylic acid is to cyanobenzene ester, the vinylformic acid pentachlorophenyl ester, methacrylonitrile, the methylacrylic acid isobornyl thiocyanoacetate, the methylacrylic acid phenyl ester, vinyl cyanide, isobornyl acrylate, vinylformic acid is to cyanobenzene ester, vinylformic acid 2-chloro-ethyl ester, methylacrylic acid 2-chloro-ethyl ester, vinylformic acid 2-naphthyl ester, positive N-isopropylacrylamide, methylacrylic acid 1-methyl fluoride ester, methylacrylic acid isopropyl ester and methylacrylic acid 2-hydroxy propyl ester.In an embodiment preferred of the present invention, polymeric material comprises poly-(methyl methacrylate), the particle of polystyrene, poly-p-methylstyrene, poly-tertiary butyl acrylamide or poly-(vinylbenzene-altogether-methyl methacrylate).In a preferred embodiment, polymkeric substance can comprise polyester.In another preferred embodiment, polymkeric substance can comprise vinyl polymer.In another preferred embodiment, polymkeric substance can comprise polyolefine.Preferred polymkeric substance can also comprise the polymkeric substance by chain polymerization reaction or step-by-step polymerization prepared in reaction.
The example of useful thermoplastic resin can be that polylactone is as poly-pivalolactone, polycaprolactone etc., reaction deutero-urethane by vulcabond and line style long chain diol, described vulcabond for example has 1, the 5-naphthalene diisocyanate, to phenylene vulcabond, between-phenylene vulcabond, 2, the 4-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 4,4 '-phenylbenzene isopropylidene vulcabond, 3,3 '-dimethyl-4,4 '-diphenyl diisocyanate, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, the dianisidine vulcabond, the tolidine vulcabond, hexamethylene diisocyanate, 4,4 '-two isocyanato ditanes etc., described line style long chain diol for example is poly-(tetramethylene adipate), poly-(ethylene glycol adipate(EGA)), poly-(hexanodioic acid 1, the 4-butanediol ester), poly-(succsinic acid glycol ester), poly-(succsinic acid 2, the 3-butanediol ester), polyether glycol etc., polycarbonate is as poly-(two (4-phenyl) carbonic ethers of methane), poly-(1, two (4-phenyl) carbonic ethers of 1-ether), poly-(two (4-phenyl) carbonic ethers of ditane), poly-(1, two (4-phenyl) carbonic ethers of 1-hexanaphthene), poly-(2, two (4-hydroxy phenyl) propane of 2-) carbonic ether etc., polysulfones, polyether-ether-ketone, polymeric amide is as (4-aminobutyric acid), poly-(hexylidene adipamide), poly-(6-aminocaprolc acid), poly-(an xylylene adipamide), poly-(to xylylene sebacoyl amine), poly-(2,2,2-tri-methyl hexamethylene terephthalamide), poly-(metaphenylene isophthaloyl amine) (Nomex ), poly-(to the phenylene terephthalamide) (Kevlar ) etc., polyester is as poly-(nonane diacid glycol ester), poly-(1, the 5-(ethylene naphthalate)), poly-(2, the 6-(ethylene naphthalate)), poly-(terephthalic acid 1,4 cyclohexane dimethanol ester), poly-(oxybenzene formic acid glycol ester) (A-Tell ), poly-(p-Hydroxybenzoate) (Ekonol ), poly-(terephthalic acid 1,4-cyclohexylidene diformazan alcohol ester) (Kodel ) (cis), poly-(terephthalic acid 1,4-cyclohexylidene diformazan alcohol ester) (Kodel ) (trans), polyethylene terephthalate, polybutylene terephthalate etc., poly-(arylidene oxygen) as poly-(2,6-dimethyl-1,4-phenylene oxygen), poly-(2,6-phenylbenzene-1,4-phenylene oxygen) etc., poly-(arylene sulfide) is as poly-(poly (phenylene sulfide)) etc., polyetherimide, vinyl polymer and their multipolymer such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral acetal, polyvinylidene dichloride, vinyl-vinyl acetate copolymer etc., polyacrylic, polyacrylate(s) and their multipolymer such as polyethyl acrylate, the positive butyl ester of polyacrylic acid, polyisobutene acid methyl esters, the polyisobutene acetoacetic ester, the positive butyl ester of polyisobutene acid, polyisobutene acid n-propyl, polyacrylamide, polyacrylonitrile, polyacrylic acid, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile copolymer, methyl methacrylate-styrol copolymer, ethylene-ethyl acrylate copolymer, iso-butylene acidifying butadiene-styrene copolymer etc., polyolefine is low and high density polyethylene(HDPE) as (straight chain), polypropylene, Chlorinated Low Density Polyethylene, poly-(4-methyl-1-pentene), polyethylene, polystyrene etc., the polymkeric substance that contains ionic linkage, Polyglycol 166-450, urethane be glycol such as glycerine for example, TriMethylolPropane(TMP), 1,2, the 6-hexanetriol, sorbyl alcohol, tetramethylolmethane, polyether glycol, polyester polyols etc. and polyisocyanates are as 2,4-tolylene vulcabond, 2,6-tolylene vulcabond, 4, the 4-'-diphenylmethane diisocyanate, 1, the 6-hexylidene diisocyanate, 4, the polymeric reaction product of 4 '-dicyclohexyl methane diisocyanate etc., polysulfones be as 2, the sodium salt and 4 of two (4-hydroxy phenyl) propane of 2-, the reaction product of 4 '-dichloro diphenyl sulfone, furane resin are as poly-furans, cellulose ester plastics such as cellulose acetate, cellulose acetate butyrate, cellulose propionate etc., siloxanes such as polydimethylsiloxane, polydimethylsiloxane, poly-(dimethyl siloxane common-phenyl methyl siloxanes) etc., protein plastic, polyethers, polyimide, poly-vinylidene halide, polycarbonate, polyphenylene sulphur, tetrafluoroethylene, polyacetal, polysulfonates, the polyester ionomer, polyolefin ionomers.Multipolymer and/or above-mentioned these mixture of polymers also can be used.
Can be used for implementing vulcanizable thermoplastic elastomer of the present invention also can change flexibly.The example of these rubber can be a brominated butyl rubber, chlorinated butyl rubber, polyurethane elastomer, fluoroelastomer, polyester elastomer, the butadiene/acrylonitrile elastomerics, silicone elastomer, polyhutadiene, polyisobutene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, sulfonated ethylene-propylene-diene terpolymer, sovprene, poly-(2, the 3-dimethylbutadiene), poly-(divinyl-pentadiene), chlorosulfonated polyethylene, the polysulphide elastomerics, by such as polystyrene, polyvinyl-toluene, glassy or crystalloid block such as poly-t-butyl styrene and polyester and such as polyhutadiene, polyisoprene, ethylene-propylene copolymer, ethylene-butene copolymer, the segmented copolymer that the segment of elastomeric block such as polyether ester constitutes, for example multipolymer in poly-(vinylbenzene)-poly-(divinyl)-poly-(vinylbenzene) segmented copolymer of the commodity Kraton  by name that makes by Shell chemical company.Can use the multipolymer and/or the mixture of above-mentioned these polymkeric substance.Preferred matrix polymer of the present invention is the polymkeric substance and the multipolymer of thermoplastic polymer such as polymeric amide, polyester and alpha-beta unsaturated monomer.
Can be used for polymeric amide of the present invention is synthetic straight chain polycarbonamide, it is characterized in that existing the integral part of multiple carboxamide group as polymer chain, and described group is each other by at least two carbon atoms separate.Such polymeric amide comprises the polymkeric substance that is called nylon in the present technique, can be obtained by the diprotic acid of diamines with the repeating unit with following general formula representative:
-NHCOR 1COHNR 2-
R wherein 1Can be at least 2, the alkylidene group of preferred 2-11 carbon atom perhaps has at least 6 carbon atoms, the arylidene of preferred 6-17 carbon atom, and R 2Can be selected from R 1And aryl.Also comprise by currently known methods, for example the copolyamide and the ternary polymeric amide that obtain of the condensation of the mixture of the diprotic acid of forming by hexamethylene-diamine with by terephthalic acid and hexanodioic acid.Above-mentioned polymeric amide is known in present technique, comprise for example copolyamide of 30% m-phthalic acid hexanediamine salt and 70% nylon salt, poly-(hexa-methylene adipamide (nylon 6,6), poly-(hexa-methylene sebacoyl amine) (nylon 6,10), poly-(hexa-methylene isophthaloyl amine), poly-(hexa-methylene terephthalamide), poly-(inferior heptyl pimeloyl amine) (nylon 7,7), poly-(octylene suberamide) (nylon 8,8), poly-(nonamethylene azelaoyl amine) (nylon 9,9), poly-(inferior decyl azelaoyl amine) (nylon 10,9), poly-(inferior decyl sebacoyl amine) (nylon 10,10), poly-(two (4-aminocyclohexyl) methane-1,10-decane-methane amide)), poly-(an xylylene adipamide), poly-(to xylylene sebacoyl amine), poly-(2,2,2-tri-methyl hexamethylene terephthalamide), poly-(piperazine sebacoyl amine), poly-(to the phenylene terephthalamide), poly-(metaphenylene isophthaloyl amine) or the like.
Other useful polymeric amide can be by amino acid and derivative thereof, those that form as the polymerization of lactan.The example of the polymeric amide that these are useful has poly-(4-aminobutyric acid) (nylon 4), poly-(6-aminocaprolc acid) (nylon 6), poly-(7-aminoheptylic acid) ((nylon 7), poly-(8-aminocaprylic acid) (nylon 8), poly-(9 aminononanoic acid) (nylon 9), poly-(the amino capric acid of 10-) (nylon 10), poly-11-aminoundecanoic acid (Ni Long11), poly-12 (nylon 12) or the like.
Be used to form the preferred polymeric amide of the used particulate of the present invention and comprise polycaprolactam, poly-(12), poly-(hexa-methylene adipamide), poly-(an inferior dimethylbenzene adipamide) and gather (6-aminocaprolc acid) and their multipolymer and/or mixture, because they are widely used and effectively in the present invention.
Can be used for implementing other polymkeric substance of the present invention is the straight chain polyester.Polyester type is unimportant, and the specific polyester of selecting to be used for any specific occasion depends on the desired physicals of final form and feature, i.e. tensile strength, modulus etc. substantially.Therefore, the extensive multiple straight chain thermoplastic polyester that changes of physicals is applicable to the present invention.
The specific polyester of selecting to use can be equal polyester or copolyesters, can be their mixture if necessary.Polyester generally can prepare by organic dicarboxylic acid and organic diol condensation.The example of useful polyester as below this paper about as described in these two pure and mild dicarboxylic acid precursor.
Be applicable to polyester of the present invention for by aromatic series, cyclic aliphatic and aliphatic diol and aliphatic series, aromatic series and cycloaliphatic dicarboxylic acid's condensation deutero-material, and can be cyclic aliphatic, aliphatic series or aromatic polyester.The useful cyclic aliphatic that can in practice of the present invention, use, the example of aliphatic series and aromatic polyester is a polyethylene terephthalate, the poly terephthalic acid cyclohexanedimethanoester ester, poly-(dodecanedioic acid glycol ester), polybutylene terephthalate, PEN, poly-(2, the 7-(ethylene naphthalate)), poly-m-phthalic acid resorcinol, poly-glycolic acid, polydiethylene glycol succinate, polyethylene glycol adipate, polyethylene glycol sebacate, poly-(nonane diacid decanediol ester), polyethylene glycol sebacate, polydecamethylene adipate, poly-sebacic acid decanediol ester, poly-(dimethyl propylene lactone), poly-(p-Hydroxybenzoate) (Ekonol ), poly-(oxybenzene formic acid glycol ester) (A-tell ), poly-(ethylene isophthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(terephthalic acid hexylene glycol ester), poly-(terephthalic acid decanediol ester), poly-(terephthalic acid 1, the 4-cyclohexanedimethanoester ester) (trans), poly-(1, the 5-(ethylene naphthalate)), poly-(2, the 6-(ethylene naphthalate)), poly-(terephthalic acid 1,4-cyclohexanedimethanoester ester (Kodel ) (cis) and poly-(terephthalic acid 1,4-cyclohexylidene diformazan alcohol ester) (Kodel ) (trans).
The present invention preferably uses the petchem that is prepared by two pure and mild aromatic dicarboxylic acid condensations.The example of these useful aromatic carboxylic acids is terephthalic acid, m-phthalic acid, phthalic acid, 1,3-naphthalic acid, 1,4-naphthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-sulfobenzide dioctyl phthalate, 1,1,3-trimethylammonium-5-formic acid-3-(to carboxyl phenyl) 1,2-indane (idane), phenyl ether 4,4 '-dioctyl phthalate, two-to (carboxyl phenyl) methane etc.In the above-mentioned aromatic dicarboxilic acid, be preferred for implementing the present invention based on the dioctyl phthalate (as terephthalic acid, m-phthalic acid, phthalic acid) of phenyl ring.In these preferred acid precursor, terephthalic acid is particularly preferred acid precursor because it cause polyester during melt-processed, to be difficult for degraded and size more stable.
Be used to implement preferred polyester of the present invention and comprise poly-polyethylene terephthalate, polybutylene terephthalate, poly-(terephthalic acid 1,4-cyclohexylidene diformazan alcohol ester) and PEN and their multipolymer and mixture.Polyethylene terephthalate most preferably in selected these polyester is because it has good physical strength, manufacturability and effective in the present invention.
The polyreaction that another kind of useful thermoplasticity polymers can pass through the alpha-beta unsaturated monomer of following formula forms.
R 3R 4C＝CH 2
R 3And R 4Can be identical or different, and can be cyano group, phenyl, carboxyl, alkyl ester, halogen, alkyl, the alkyl that replaced by one or more chlorine, fluorine or hydroxyl.The example of these preferred polymkeric substance is following polymer of monomers: ethene, propylene, hexene, butylene, octene, vinyl alcohol, vinyl cyanide, vinylidene halide, acrylate, methylacrylate, tetrafluoroethylene, a chlorotrifluoroethylene, vinylchlorid, vinylbenzene etc.The multipolymer of above-mentioned polymkeric substance and/or mixture also can be used for the present invention.
Being used to implement the preferred thermoplastic that forms by the alpha-beta polymerization of unsaturated monomers of the present invention is polypropylene, polyethylene, polystyrene and their multipolymer and/or mixture, wherein most preferably polyacrylic polymer and multipolymer are because their costs are low and have favorable mechanical and a surface property.
The synthetic polymer that another group can be used as polymkeric substance of the present invention comprises thermoset copolymer material such as polyester, unsaturated polyester, alkyd, novolac polymer, aminoplastics, Resins, epoxy, urethane and polysulphide.
Be used to form the used particulate polymkeric substance of the present invention and can comprise polymer monomer.In a preferred embodiment, this monomer can be vinyl monomer.Preferred vinyl monomer can comprise methyl methacrylate, ethyl methacrylate, butyl isocrotonate, ethyl propenoate, butyl acrylate, Ethyl acrylate, the vinylformic acid n-octyl, the methylacrylic acid lauryl, methylacrylic acid 2-ethylhexyl, vinylformic acid ester in the ninth of the ten Heavenly Stems, the iso-butylene acid benzyl ester, methylacrylic acid 2-hydroxy propyl ester, vinyl cyanide, methacrylonitrile, vinyl-acetic ester, propionate, vinylidene chloride, vinylchlorid, vinylbenzene, t-butyl styrene, Vinyl toluene, divinyl, the vinyl-chloride-containing base, isoprene, N, the N-DMAA, vinylformic acid, methylacrylic acid, the chloro methylacrylic acid, toxilic acid, allyl amine, N, N-diethyl allyl amine, the vinyl sulphonamide, sodium acrylate, SODIUM METHACRYLATE, the methylacrylic acid ammonium, ammonium acrylate, acrylamido propane-triethyl ammonium chloride, methacrylamido propane-triethyl ammonium chloride, vinyl-pyridine hydrochloride, vinyl phosphonate sodium, 1-methyl ethylene Alendronate, sodium vinyl sulfonate, 1-methyl ethylene-sodium sulfonate and Sodium styrene sulfonate.
This monomer can also comprise the functional monomer.In a preferred embodiment, this functional monomer comprise contain at least one be selected from list-COOH, many-COOH ,-COOH salt, NH 2, acid anhydride, epoxy group(ing), acyl chlorides, sulfonic acid, sulfonate and OH member's monomer.
Any charged or uncharged stablizer all can be used for forming particle of the present invention.These examples charged or uncharged stablizer include but not limited to carboxylic acid, sulfonate or polyoxyethylene.Stablizer can comprise tensio-active agent, and described tensio-active agent can be the tensio-active agent of electronegative electricity, tensio-active agent or uncharged tensio-active agent of positively charged.In one embodiment, tensio-active agent can be a monomer.Useful ionic compound can be a cats product, comprises sulfonium derivative, phosphine class and the sulfide of compounds such as ammonium (primary, secondary, uncle and Ji), phosphorus or aliphatic series, aromatic series or aryl aliphatic amine.Typical ion can cause carrying out ion-exchange and inserting in the genetic horizon by the metallic cation with preferred montmorillonitic clay.
Intercalator micron or nano particle that the present invention is used can also comprise a kind of initiator.This initiator can be a kind of azo initiator, peroxide initiator, redox initiator or the like.In one embodiment, initiator can be a monomer.Use initiator can strengthen polyreaction.Possible advantage is that the clay that can be enhanced peels off or intercalation, especially can cause changing because strengthen polyreaction, and as size, molecular weight, these can cause expansion bigger between the clay thin layer.
Be most appropriate to stratified material of the present invention and comprise board-like material with remarkable high aspect ratio.But other material with high aspect ratio also is useful.Be suitable for stratified material of the present invention and comprise clay or non-clay.These materials comprise that layered silicate if you would take off stone, especially sodium montmorillonite, magnesium montmorillonite or/and Ca-montmorillonite, nontronite, beidellite, hectorite, volkonskoite, saponite, sauconite, Sobockite, stevensite, Svinfordite, vermiculite, magadiite, Kenyaite, talcum, mica, kaolinite and their mixture.Other useful stratified materials have illite, illite/smectite minerals mixture, as the mixture of Ledikite, illite and above-mentioned stratified material.The stratified material that other are useful, particularly the stratified material that uses with positively charged ion matrix polymkeric substance is lamellated double-hydroxide clay or hydrotalcite, as Mg 6Al 3.4(OH) 18.8(CO 3) 1.7H 2O, it has the commutative negatively charged ion in positive charge layer and the space, middle layer.They have on other layer seldom or do not have the stratified material of electric charge also can use, as long as can insert their middle layer spatial swelling agent of expansion.These stratified materials comprise for example FeCl of muriate 3, FeOCl, chalcogenide is for example as TiS 2, MoS 2And MoS 3, prussiate is Ni (CN) for example 2With oxide compound H for example 2Si 2O 5, V 6O 13, HTiNbO 5, Cr 0.5V 0.5S 2, V 2O 5, doping Ag V 2O 5, W 0.2V 2.8O 7, Cr 3O 8, MoO 3(OH) 2, VOPO 4-2H 2O, CaPO 4CH 3-H 2O, MnHAsO 4-H 2O, Ag 6MO 10O 33Deng.Preferred stratified material is expandable, thereby other reagent is generally organic ion or molecule, just can be inserted into and/or peel off stratified material, and forms the dispersion of the inorganic phase of ideal.These expandable stratified materials comprise 2: 1 type layered silicates, (see also " clay colloid chemistry brief introduction (An introduction to clay colloid chemistry), H.Van Olphen, Jchn Wiley as defining in the literature; SonsPublishers).The typical layered silicate that preferably has 50 to 300 milliequivalents/100g cation exchange capacity (CEC).Be preferred for stratified material of the present invention and comprise clay, particularly for example nontronite, nontronite, beidellite, inscription mountain range stone, button montmorillonite, saponite, hectorite, aluminium soap stone (soboekite), richness are waited montmorillonite, svinfoMite, halloysite, natural water glass, fibrous morphology crystals and vermiculite and layered double-hydroxide or hydrotalcite to montmorillonitic clay.Most preferred stratified material comprises montmorillonite, hectorite and hydrotalcite, because be available on the industry on these materials.
Aforesaid montmorillonitic clay can be natural or synthetic, for example synthetic montmorillonite stratiform material.This difference can influence the content of particle diameter and/or related impurities.In general, the synthesis of clay lateral dimension is littler, and therefore has littler aspect ratio.But synthesis of clay and natural clay are comparatively speaking purer, have narrower distribution of sizes, may not need further purifying or separation.For the present invention, the lateral dimension that suitable clay particle has is 0.01 μ m to 5 μ m, is preferably 0.05 μ m to 2 μ m, more preferably 0.1 μ m to 1 μ m.The thickness of clay particle or vertical dimension can change between 0.5nm to 10nm, are preferably 1nm to 5nm.For the present invention, as the aspect ratio of the ratio of the minimum and maximum size of clay particle should be＞10: 1, preferred＞100: 1, more preferably＞1000: 1.Aforementioned restriction about particle size and shape is to be used for guaranteeing that some aspect of performance in nano composite material has enough improvement and can adverse influence do not arranged to other performance.For example big lateral dimension can cause aspect ratio to rise, and this improvement for machinery and barrier properties is an ideal.But very large particle can cause optical defect, optical haze for example, and may wear and tear washing processing, transmission and finish machining equipment and imaging layer.
Being used for clay of the present invention can be organic clay.Organic clay can be produced by not functionalized clay and suitable inset reaction.These insets are generally organic compound, and it can be neutral or ionic.Useful neutral organic molecule comprises polar molecule such as acid amides, ester, lactan, nitrile, urea, carbonic ether, phosphoric acid ester, phosphonic acid ester, sulfuric ester, sulphonate, nitro-compound or the like.
Being suitable for commercially available clay of the present invention has the clay of Laponite , Nanoclay , Claytone  and Permont  family.For purposes of the invention, Laponite  RDS is preferred clay, synthetic li-montmorillonite clay in the montmorillonitic clay family.NaCloisite  is preferred natural montmorillonitic clay, and perhaps Nanoclay also belongs to montmorillonitic clay family.
The intercalated particles that the present invention adopts can be passed through emulsion polymerization prepared, as P.A.Lovell, and M, S, " letex polymerization and emulsion polymer (the EmulsionPolymerization and Emulsion Polymer) " that EL-Aassar, John, Wiley and Sons (1997) write is described.The intercalation polymeric composition granule also can react by a series of polyreactions or step-by-step polymerization and prepare.Particle can prepare by grinding polymkeric substance and dispersion agent in medium, and wherein polymkeric substance is insoluble to medium.By grinding with grinding medium or the milled solid particle prepares particle.Can prepare particle by make insoluble polymer emulsification with surfactant/dispersant.Can also prepare particle by the following method: be used in dispersion agent in the medium and make and contain the emulsification of solvent polymeric thing, wherein polymkeric substance is insoluble to medium, and removes and desolvate.
Intercalation material, preferred nano composite material can be by any method preparation that can prepare micron or nano particle in water or in the organic solvent, and these materials are applied to the present invention.In a suitable embodiment, the method that is used to prepare nano composite material comprises the following steps: to prepare the particle that a kind of diameter is equal to or less than 3 nanometers, with this particle and the stratified material mixture that is dispersed in the medium, and insert stratified material to produce nano composite material.The method that another kind of suitable being used for prepares nano composite material comprises the following steps: to prepare the particle that a kind of diameter is equal to or less than 3 microns by mixing and emulsifying polymerization reaction monomer and the tensio-active agent that is dispersed in medium, wherein this monomer can not be scattered in the medium, this particle is mixed with the stratiform in being dispersed in medium, and insert stratified material to produce a kind of nano composite material.In another suitable embodiment, can prepare nano composite material by the following method: in medium, grind polymkeric substance and tensio-active agent, described tensio-active agent is insoluble to medium, wherein this polymkeric substance can not be scattered in the medium, thereby form diameter and be equal to or less than 3 microns particle, it is dispersed in the medium, particle is mixed with stratified material in can being dispersed in this medium, and insert stratified material to produce a kind of nano composite material.Another suitable embodiment comprises a kind of method for preparing nano composite material, described method comprises the following steps: to be used in the solvent-laden polymkeric substance of emulsifying agent emulsification in the medium, wherein this polymkeric substance can not loose in this medium, remove and desolvate to form the particle that a kind of diameter is equal to or less than 3 microns, particle is mixed with the stratified material that can be dispersed in the medium, and insert stratified material to produce a kind of nano composite material.
The medium that is used for discrete particles and material that is preferred for preparing the used nano composite material of the present invention can comprise water-bearing media, organic solvent or polymkeric substance or their mixture.
This intercalation material of the present invention can use separately, as application element, image-forming component, viscosity modifier etc.Intercalation material of the present invention can also form object with substrate combination.In a preferred embodiment, particle comprises matrix and inserts the stratified material that is dispersed in the polymer beads in the medium.
In a preferred embodiment, matrix comprises at least a polymkeric substance.Matrix polymer can be the above-mentioned intercalator particulate polymkeric substance of any aforementioned this paper of being used to form.Polymkeric substance can be any natural or synthetic polymer.Matrix polymer can also be any water-soluble or insoluble polymkeric substance.Most preferred water-soluble polymers preferably includes gelatin, polyvinyl alcohol, polyethylene oxide, Polyvinylpyrolidone (PVP), polyacrylic acid, polystyrolsulfon acid, polyacrylamide and quaternary ammonium polymer.Used matrix polymer can be with identical or different as the polymkeric substance of above-mentioned intercalation polymeric thing.Preferred matrix polymer can comprise polyester, polyolefine, polystyrene or polymeric amide.Matrix polymer is a thermosetting polymer, for example unsaturated polyester, Synolac, resol, aminoplastics, Resins, epoxy, urethane and poly-sulphur thing.In a preferred embodiment, matrix polymer can be a polyethylene terephthalate.
Can stratified material and micron particle of the present invention or nano particle be interacted to insert/to peel off by the known method for preparing nano composite material in any present technique.Adding stratified material, micron particle or nano particle and optional accrete order and method can change.
Contain stratified material and can be by any suitable method formation with the material of the present invention of the micron particle of optional annexation or nano particle; for example extrude, through or without the coextrusion of single shaft or diaxial orientation, while or continuously elongated, blowing, injection moulding, lamination, solvent cast etc.
Above-mentioned optionally additive can include but not limited to nucleator, filler, softening agent, impact modifying agent, chainextender, tinting material, slipping agent, static inhibitor, pigment such as titanium oxide, zinc oxide, mica, lime carbonate, dispersion agent such as fatty amide (as stearylamide), the metal-salt of lipid acid such as Zinic stearas, Magnesium Stearate, dyestuff such as ultramarine blue, cobalt violet, antioxidant, white dyes, UV light absorber, fire retardant, roughening agent (roughening agen), linking agent, pore former or the like.Select optional annexation and their corresponding quantity as required.
Stratified material of the present invention and particle or nano particle can also interact with matrix polymer by known any suitable method in the technology of preparation nano composite material.Adding stratified material, micron particle or nano particle, matrix and optional accrete order can change.
In one embodiment, can be earlier stratified material be mixed with suitable micron particle or nano particle, mix with matrix then.In another embodiment, stratified material can be mixed simultaneously with the micron particle or the nano particle that suit.In another embodiment, can be in suitable matrix monomer or oligopolymer, then by substep or chain polymerization reactive polymeric with stratified material and micron particle or nanoparticulate dispersed.In another embodiment, the stratified material that inserts micron particle or nano particle can be a kind of monomer, and it can participate in polyreaction to form matrix material with matrix.In another embodiment; can be with stratified material and micron particle or nano particle melting mixing under the temperature that preferably is equivalent on melting point polymer or the fusing point; carry out or do not shear; under the temperature that preferably is equivalent on melting point polymer or the fusing point, matrix is mixed then, carry out or do not shear.In another embodiment, can be with stratified material and micron particle or nano particle and matrix melting mixing, its temperature preferably is equivalent to the temperature on melting point polymer or the fusing point, and carries out or do not shear.In another embodiment, stratified material and micron particle or nano particle can be made up in solvent phase realizing and insert/peel off, mix with matrix then.The solution of gained or dispersion can be used separately or remove by drying and desolvate.Solvent can be aqueous or organic solvent.Organic solvent can be a polarity or nonpolar.In another embodiment, stratified material, micron particle or nano particle and matrix can be inserted/peel off with realization with the solvent phase combination.The solution of gained or dispersion can be used separately or remove by drying and desolvate.Solvent can be moisture or organic solvent.Organic solvent can be a polarity or nonpolar.
Be to implement the present invention, expectation is guaranteed matrix polymer and is used for stratified material insertion or micron particle that peels off or the consistency between the nano particle to small part.Be purpose of the present invention, consistency refers to the miscibility of molecular level.If matrix polymer comprises mixture of polymers, then the polymkeric substance in the mixture should be compatible with the micron or the nano particle that are used for the stratified material intercalation to small part.If matrix polymer contains multipolymer, then this multipolymer should be compatible with the micron or the nano particle that are used for the stratified material intercalation to small part.
Containing stratified material, micron particle or nano particle, polymeric matrix and object of the present invention that may the bonded optionally additive can form by any suitable method, for example extrudes, passes through or without the coextrusion of single shaft or diaxial orientation, while or continuously elongated, blowing, injection moulding, lamination, solvent cast etc.
In a suitable embodiment of the present invention, can be in suitable double-screw type compounding machine and micron particle of the present invention or nano particle melting mixing with the stratified material of optional annexation, to guarantee suitable the mixing.The example of double-screw type compounding machine that is used for the experiment of following detailed description is LeistritzMicro  27.Twin screw extruder is assembled according to building block principle.Therefore, can easily change the mixing of additive, the residence time of resin and the adding point of additive by changing screw design, piping design and processing parameter.Be used to prepare other compounding machine of the present invention and include but not limited to the double-screw type compounding machine produced by Werner andPfleidener and Berstorff.The operating method of these compounding machines can be that corotation changes or despining.
The screw diameter 27mm of Leistritz mixing machine has the function length of 40 diameters.The maximum quantity of this compounding machine conduit region 10.The maximum revolution speed of screw degree of this compounding machine can be 500rpm.This double-screw type compounding machine can be furnished with the main feeder that can add resin, and can close a kind of main feeder of samarium or use two side filling machines to add additive, and screw design need suit to dispose.
The mode that preferably stratified material is added to micron particle or nano particle can be dispersed in the polymeric matrix to guarantee weighting material by using the side filling machine, and the thermal history of control additive.In this manner, can use main resin feeding device to add micron particle and nano particle, can add stratified material by the downstream side filling machine then, perhaps vice versa.Selectively, can use main feeder to add stratified material and micron particle or nano particle in same position, perhaps can be with stratified material and micron particle or nano particle pre-mixing, and by single side filling machine adding.This method particularly suitable is if only can obtain a side filling machine and limited by screw design.
Except above-mentioned compound, material of the present invention can use any suitable mixing equipment production, for example single-screw compounding machine, blending machine, mixing machine, pressing machine, forcing machine or moulding machine.
Object of the present invention can be virtually any size and shape, can be liquid such as solution, dispersion liquid, latex and analogue, also can be layer of solid such as paper, club, particle, powder, fiber, wire, pipe, cloth, non-woven fabric, upholder, multilayered structure or the like.Material of the present invention can be used for any purpose, for example packs, braiding or non-fabric protection coverlet or clothes and medical apparatus.
In an embodiment preferred of the present invention, object of the present invention comprises the matrix of image-forming component.These image-forming components comprise the element of the imaging that utilizes photograph, electrofax, eletrophotography, photothermal imaging, migration, electric heating process, dielectric medium record, heat sensitive dye transfer printing, ink-jet and other type.In an embodiment preferred of the present invention, object of the present invention comprises the matrix of photographing imaging element, and the reflection printed material of particularly taking a picture shows product as paper or other.In another preferred embodiment, this object can comprise application element.
Be used for the typical matrix bag nitrocellulose, cellulose acetate, polyvinyl acetate, polystyrene, polyolefine, polyethylene terephthalate, PEN, polycarbonate, polymeric amide, polyimide, glass of image-forming component, natural and synthetic paper, resin coating paper, hollow polymer, microporous polymer, microporous materials hollow nano polymkeric substance and nano-porous polymer, fiber etc.The material of the present invention that comprises matrix polymer and intercalation stratified material can add the matrix that any of these material and/or combination are used for suitable image-forming component.Under the situation of multilayer imaging element, above-mentioned material of the present invention can add any meaning one or more layers, and can be in imaging support Anywhere, for example in the top side or in the bottom side or in top side and bottom side, and/or between the both sides of carrier.The adding method can comprise extrude, through or without tensile coextrusion, blowing, curtain coating, curtain coating, lamination, press polish, embossing, coating, spraying, molded etc. altogether.Can be in the either side or the both sides of imaging support according to image receiving layer of the present invention.
In a preferred embodiment, the imaging support of the present invention that is used for that comprises matrix polymer and intercalation stratified material of the present invention can be by extruding and/or coextrusion, and oriented surface forms then, forms as typical photograph film matrix based on polyester.Selectively, the composition that comprises the stratified material of matrix polymer and intercalation of the present invention can be extruded and be coated on another carrier, as squeezes and typically be used for the resin that developing out paper applies operation.In another embodiment, the composition that comprises matrix polymer and intercalation stratified material of the present invention can be extruded or coextrusion, and preferred orientation is laminated to another carrier then to preformed thin slice, as the formation of typical lamination reflection print media.
In another embodiment, material of the present invention can be added be used for pictorial display imaging support as the reflection print media, comprise paper, particularly based on paper, hollow polymer and the combination thereof of resin.Selectively, imaging support can comprise the combination of reflecting medium and light transmission medium, to realize special effect, shows as day and night.In a preferred embodiment, at least one layer that comprises material of the present invention can be added to paper carrier, because it is widely used.In another preferred embodiment, the layer that at least one can be comprised nano composite material of the present invention is added to the imaging support that comprises hollow polymer, shows purposes in reflectivity, metal radiance, daytime and the evening of many perfect performance such as tear resistance, slipperiness, improvement because it has.
The imaging support of use of the present invention can comprise the supplementary layer of any amount.These supplementary layers can comprise antistatic layer, back mark retaining layer, articulamentum or short adhesive coating, wear-resistant friction layer, conducting stratum, barrier layer, confession knitting layer, uv-absorbing layer, anti-halation layer, optical effect layer, waterproof layer etc.
Object of the present invention also can be made non-imaging applications.For example, this object may comprise viscosity modifying agent, tackiness agent, engineering resin, slipping agent, mixed with polymers composition, biomaterial, water treatment additive, components of cosmetics, static inhibitor, food and drink wrapping material, semi-conductor, superconductor or be used for the compound releasing agent of medicine.
Embodiment
Following embodiment illustration application of the present invention.They do not plan all possible changing conditions of the present invention all is being described in detail.If there is not other explanation, umber and per-cent are according to the weight meter.
The micron particle and the nano particle that use are:
Table 1
Polymkeric substance ID Particle size (μ m)
????P1(PSHb/Barquat) ????0.0272
????P2(PSHbEd10G) ????0.0155
????P3(PS-E/A-246L) ????0.0264
????P4(PSHb/10G) ????0.065
????P5(PS/Barquat) ????0.0209
????P6(PS/A-246L) ????0.019
????P7 ????2
????P8 ????0.537
????P9 ????0.527
By emulsion polymerizing preparation compound particle 1
Prepare polymer beads by emulsion polymerization technology.In the 1L three-necked flask, add the Barquat (3.0g) of 80g deionized water and 50%, dispose nitrogen inlet tube, mechanical stirrer and condenser on the flask.Flask is immersed in 60 ℃ the water bath with thermostatic control, with purging with nitrogen gas 20 minutes, add Potassium Persulphate (0.35g), add then contain cinnamic monomer emulsion (56g), hydroxy acrylic acid brine (4g), Potassium Persulphate (0.35g), Barquat (50%) (3.0g), deionized water (60g) (C).Continuously stirring mixture in the interpolation process of monomer emulsion.The interpolation time of monomer emulsion is 2 hours, after the interpolation of first monomer emulsion finishes, continues polyase 13 0 minute, and mixture is cooled to room temperature, filters then.
By emulsion polymerizing preparation compound particle 2-6
Employing is similar to the method synthetic polymer particle P2-P6 of the above-mentioned particle 1 of preparation, just P2 uses Olin 10G as tensio-active agent and use glycol ester diisobutylene as linking agent, P3 uses Rhodapol A-246L as tensio-active agent, replace Hb with MAA, P4 uses Olin 10G as tensio-active agent, P5 only uses vinylbenzene, and P6 uses Rhodapol A-246L also only to use vinylbenzene as tensio-active agent.
Prepare polymer beads P7 by emulsifying process
Prepare polystyrene with solution polymerization process in toluene, solid content is 20%.Tensio-active agent Triton 770 thorough mixing with 1000g deionized water and 5.3g 30%.The 200g polystyrene solution is joined in this aqueous solution lentamente, and the while is the vigorous stirring mixture at room temperature.By violent stirring with the mixture homogenization of gained to form fine droplet.Remove volatile solvent in vacuum and 52 ℃ of following rotary evaporations.
By grinding broken prepared polymer beads P8 and P9
Polymer beads prepares by Ginding process.The polymeric grinding medium bead of 50 microns of 30g mean diameters, 30g polystyrene powder, 30% Triton 770,10.5g sodium salt and 209.5g deionized water are mixed in 2L double-walled container (available from BYK-Gardner), with high-energy medium grinder (Morehouse-Cowles Hochmeyer productions) grinding.Shredder at room temperature turned round about 8 hours.Abrasive filters by 4-8 μ m KIMAX  Buchner funnel, thereby dispersion is separated from grinding medium.The Buchner funnel derives from VWR Scientific Products company.
The stratified material that uses is:
Table 2
Stratified material ID Title Supplier (001) basic interplanar spacing (dust)
??L1 ??NaCloisite Southern Clay Products Inc. ?13
??L2 ??Laponite?RDS Southern Clay Products Inc. ?13
The characterizing method that uses comprises:
(001) basic interplanar spacing is measured with X-ray diffraction, promptly utilizes and is transferred to the alpha-emitting monochromator of CuK, uses Rigaku Bragg-Brentano diffractometer in reflective-mode geometry.All measurements are under atmospheric pressure carried out.
With transmission electron microscopy (TEM) form of stratified material is done further to estimate, promptly be used under the 200KV acceleration voltage measurement microscope of operation (JEM-2000FX from JEOL INC).Following embodiment emphasize with particle particularly polymer beads insert the observed case of stratified material.
Embodiment 1-3. inserts the Na Cloisite  of P1
At room temperature Na Cloisite  was mixed in water 18 hours with P1 solution.From each mixture, get several solution and be stacked on the independent glass slides sheet, be allowed to condition in the ambient air dry.Study the structure of the solid film that forms on the glass sample fixer by X-ray diffraction (XRD).XRD the results are shown in Table 3.
Table 3
Embodiment ????P1/L1 Spacing ( *)
????1 ????95/5 ????32，19 1
????2 ????50/50 ????17
????3 ????25/75 ????14
1 detects two in some samples inserts phase, may be because mixing is inhomogeneous, or certain regional heat-up time oversize (container bottom) of sample, the part degraded that causes inserting material.
Compare with the stratified material L1 (table 2) that reports (001) basic interplanar spacing, the basic interplanar spacing of embodiment 1-3 raises to some extent, shows that intercalation takes place as inserting and/or peeling off.These results have been confirmed by TEM.
Embodiment 4-6, the Na Cloisite  of insertion P2
At room temperature clay Na Cloisite  was mixed in water 24 hours with the polymer latex liquid solution, from each mixture, get several solution and be stacked on the independent glass slides sheet, be allowed to condition in the ambient air dry.The structure of the solid film that forms on the XRD research glass sample fixer.XRD analysis the results are shown in Table 4
Table 4
Embodiment ????P2/L1 Spacing ( *)
????4 ????95/5 ????19
????5 ????50/50 ????17
????6 ????25/75 ????14
Compare with (001) basic rich interplanar spacing of the stratified material L1 (table 2) that reports, the basic interplanar spacing of embodiment 4-6 rises to some extent, shows that intercalation takes place as inserting and/or peeling off.TEM has confirmed these results.
Embodiment 7-14, the clay of insertion polymerization thing
At room temperature 5 parts of Na Cloisite  or Laponite  were mixed 18 hours with 95 parts of polymer beads that are dispersed in the water, from each mixture, get several solution and be stacked on the independent glass slides sheet, be allowed to condition in the ambient air dry.The structure of the solid film that forms on the XRD research glass sample fixer.XRD analysis the results are shown in Table 5
Table 5
Embodiment ????P ????L Spacing ( *)
????7 ????P3 ????L2 Do not observe the peak
????8 ????P4 ????L2 Do not observe the peak
????9 ????P1 ????L2 19.3, stratification
????10 ????P4 ????L1 19.3, stratification
????11 ????P3 ????L1 Stratification
????12 ????P2 ????L2 Stratification
????13 ????P5 ????L1 ????32，18 1
????14 ????P6 ????L1 ????35
1 detects two in some samples inserts phase, may be because blended is inhomogeneous, or certain regional heat-up time oversize (container bottom) of sample, the part degraded that causes inserting material.
Compare with the stratified material L1 (table 2) that reports (001) basic interplanar spacing, embodiment 7-14 represents the evidence that basic interplanar spacing rises to some extent, shows that intercalation takes place as inserting and/or peeling off.Fig. 1 illustrative examples 8 does not have (001) basic plane X-ray diffraction peaks.When inserting (peeling off) fully, as embodiment 8, stratified material is pushed and leaves certain distance, thereby makes them be seen as the set of the thin slice of stratified material thin layer, each thin layer is corresponding to the independent layer of this material, and each thin layer does not take place significantly to interact with any adjacent stratified material.When measuring the spacing of an exfoliation material, do not observe the peak.
Fig. 2, the TEM figure of example 8 show that Laponite (R) clay peels off into independent thin slice, and this is consistent with the same material XRD figure that Fig. 1 shows.
Notice that further the exfoliated clay thin slice may be in a particular manner and crosslinked polymer.Polymkeric substance itself is spherical in shape, similar pearl shape on the form, and diameter is between about 30-80nm.The Laponite that peels off (R) clay gall or stick to polymer beads surface or be inserted between bead and the bead is seen Fig. 2.
Fig. 3 illustrates the influence of 3 couples of L1 of polymer beads, and the L1 that does not contain polymkeric substance has (001) basic plane X-ray diffraction peaks, and Fig. 3 A has the spacing of 13 dusts.Polymer beads P3 is mixed with L1, cause the disappearance of (001) basic plane X-ray diffraction peaks, Fig. 3 B shows that L1 almost completely inserts (peeling off).The same material XRD figure that the data of TEM and Fig. 3 B show is in full accord.
Example 15-17 inserts the clay of PET
At room temperature 5 parts of Na Cloisite  were mixed 18 hours with 95 parts of PET particles that are dispersed in the water.From each mixture, get several solution and be stacked on the independent glass slides sheet, be allowed to condition in the ambient air dry.The structure of the solid film that forms on the XRD research glass sample fixer.XRD analysis the results are shown in Table 6
Table 6
Embodiment ????P ????L Spacing ( *)
????15 ????P8 ????L1 ????27
????16 ????P9 ????L1 ????22
Compare with the stratified material L1 (table 2) that reports (001) basic interplanar spacing, embodiment 15-16 represents the evidence that basic interplanar spacing rises to some extent, shows that stratification takes place as inserting and/or peeling off.
Example 17 clays are aggregated the expansion of thing grain
At room temperature, 4 parts of Na Cloisite  were mixed 18 hours with 96 parts of polymer beads that are dispersed in the water, from each mixture, get several solution and be stacked on the independent glass slides sheet, be allowed to condition in the ambient air dry.The structure of the solid film that forms on the XRD research glass sample fixer.XRD analysis the results are shown in Table 7.
Embodiment ????P ????L Spacing ( *)
??17 ????P7 ????L1 ????23
Compare with the stratified material L1 that reports (001) basic interplanar spacing, the evidence that the basic interplanar spacing of embodiment 17 expressions rises to some extent shows that stratification takes place as inserting and/or peeling off.

Claims (10)

1. intercalation material, this intercalation material comprise and insert a kind of particulate stratified material, and wherein this particulate diameter is equal to or less than 3 microns.
2. the material of claim 1, wherein this particle comprises the micron particle that diameter is the 0.5-3 micron.
3. the material of claim 1, wherein this particle comprises diameter less than 0.5 micron nano particle.
4. the material of claim 1, wherein this stratified material is a clay.
5. the material of claim 1, wherein this stratified material comprises at least a following member: the FeCl that is selected from 3, FeOCl, TiS 2, MoS 2, MoS 3, Ni (CN) 2, H 2SiO 5, V 6O 13, HTiNbO 5, Cr 0.5V 0.5S 2, mix silver-colored V 2O 5, V 2O 5, W 0.2V 2.8O 7, Cr 3O 8, MoO 3(OH) 2, VOPO 4-2H 2O, CaPO 4CH 3-H 2O, MnHASO 4-H 2O and Ag 6Mo 10O 33
6. object, this object comprise matrix and insert the stratified material that is dispersed in the polymer beads in the medium.
7. method for preparing nano composite material, described method comprises the following steps: to prepare a kind of particle, this particle is mixed with stratified material in being dispersed in medium, and this stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.
8. method for preparing nano composite material, described method comprises the following steps: to prepare a kind of particle by mixed emulsion polymerization single polymerization monomer and the tensio-active agent that can be dispersed in the medium, wherein this monomer can not be scattered in this medium, this particle and the stratified material that is dispersed in this medium are mixed, and this stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.
9. method for preparing nano composite material, described method comprises the following steps: to grind this polymkeric substance in polymkeric substance can not the dispersive medium and can be distributed to tensio-active agent in this medium to form a kind of particle that is dispersed in this medium, this particle is mixed with stratified material in can being distributed to this medium, and this stratified material carried out intercalation to produce a kind of nano composite material, wherein this particulate diameter is equal to or less than 3 microns.
10. method for preparing nano composite material, described method comprises the following steps: to make with tensio-active agent in polymkeric substance can not the dispersive medium solvent-laden polymer emulsified, and remove and desolvate to form a kind of particle, this particle and the stratified material that can be distributed in this medium are mixed, and this stratified material carries out intercalation to produce a kind of nano composite material, and wherein this particulate diameter is equal to or less than 3 microns.
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